CN102603810B - The preparation method of rare earth compounding and preparation method thereof, polymerization catalyst system and preparation method thereof, polymkeric substance - Google Patents

The preparation method of rare earth compounding and preparation method thereof, polymerization catalyst system and preparation method thereof, polymkeric substance Download PDF

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CN102603810B
CN102603810B CN201210020478.1A CN201210020478A CN102603810B CN 102603810 B CN102603810 B CN 102603810B CN 201210020478 A CN201210020478 A CN 201210020478A CN 102603810 B CN102603810 B CN 102603810B
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崔冬梅
潘玉鹏
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a kind of rare earth compounding and preparation method thereof, the method synthesis is simple, and yield is up to 45% ~ 67%.The present invention also provides a kind of polymerization catalyst system and preparation method thereof.The present invention also provides a kind of preparation method of polystyrene, and monomer conversion reaches as high as 100%, and activity reaches as high as 1.25 × 10 7g mol ln -1h -1, between synthesized polystyrene, normality (rrrr) reaches as high as 100%, and number-average molecular weight is in 4.6 ~ 1,000,000 scopes, and molecular weight distribution is minimum reaches 1.20.This polymerization catalyst system Butadiene and cinnamic copolymerization, copolymer characteristic is polystyrene segment is isostructure; Polybutadiene segments is mainly along Isosorbide-5-Nitrae-structure, reaches 99.3%; Utilize the styrene catalyzed polyisoprene segments obtained with the polyreaction of isoprene of this polymerization catalyst system to be mainly 3,4-structure, can 73.5% be reached.

Description

The preparation method of rare earth compounding and preparation method thereof, polymerization catalyst system and preparation method thereof, polymkeric substance
Technical field
The present invention relates to catalyst technical field, more particularly, relate to the preparation method of a kind of rare earth compounding and preparation method thereof, polymerization catalyst system and preparation method thereof, polymkeric substance.
Background technology
According to the difference of steric configuration, polystyrene is divided into random polystyrene, syndiotactic polystyrene and isotactic polyphenylacetylene.The synthesis of polystyrene realizes mainly through radical polymerization, anionoid polymerization, cationoid polymerisation and Ziegler-Natta catalyst catalyzed polymerization.Traditional radical polymerization, anionoid polymerization and cationoid polymerisation mainly obtain random polystyrene, and Ziegler-Natta catalyst is polymerizing styrene catalyzed mainly obtains isotactic polyphenylacetylene.In the regioselectivity and stereoselectivity control of polymkeric substance, compared with uncontrollable with the selectivity of anionoid polymerization, polycoordination has obviously advantage.Syndiotactic polystyrene, owing to having the characteristics such as high-melting-point, high crystalline, high elastic coefficient, low-k, low loss factors and excellent heat-resisting solvent resistant, industrially becomes a kind of material had a great attraction.
High syndiotactic polystyrene was realized by using the metallocene catalyst catalyzed polymerization of titanium by Japanese Idemitsu Kosan company first in 1986.Since the styrene catalyzed high syndiotactic polymerization of Japanese Idemitsu Kosan company invention titanium complex energy in 1986, investigators develop titanium catalyst system in succession, such as, and Cp*TiCl 3/ MAO and Cp*TiR 3/ B (C 6f 5) 3to have during styrene polymerization very high catalytic activity and have simultaneously very high between normality.There is a small amount of report the polymerizing styrene catalyzed aspect of rare earth metal complex.Such as, some study group report rare earth metal complex and can obtain random polystyrene to be low to moderate moderate living polymerization vinylbenzene.The alkylate that Yasuda study group reports single luxuriant lanthanum obtains rich syndiotactic polystyrene with lower living polymerization vinylbenzene.Within 2000, Wakatsuki study group reports samarium complex with very high active catalytic polymerizing styrene, but the polystyrene obtained is random.Until 2004, the styrene catalyzed high syndiotactic polymerization of rare earth metal complex just achieves important breakthrough truly.Carpentier study group reports rare earth metal allylation compound [Cp-CMe 2-Flu] Ln (C 3h 5) (THF) to place an order component catalyst vinylbenzene height syndiotactic polymerization at the polymerization temperature of 60 DEG C, polyreaction has very high activity, and between the polystyrene obtained, normality (rrrr) reaches as high as 100%, and fusing point is within the scope of 257 ~ 263 DEG C.Almost simultaneously, Hou study group reports single cyclopentadienyl rare-earth metal alkylate (C 5me 4siMe 3) Ln (CH 2siMe 3) 2(THF) under the effect of organic boron salt, double-component catalyst vinylbenzene height syndiotactic polymerization, polymerization activity is 1.36 × 10 7g mol ln -1h -1, between the polystyrene obtained, normality (rrrr) reaches as high as 100%, and fusing point is within the scope of 268 ~ 273 DEG C.Subsequently, styrene catalyzed high syndiotactic polymerization under some rare earth metal complexs having a luxuriant or assorted cyclopentadienyl ligand are also reported in promotor effect.But the application of rare earth metal complex in vinylbenzene height syndiotactic polymerization having constrained geometry configuration part rarely has report, the exploitation having the catalyst system of the rare earth metal complex of constrained geometry configuration part has very large academic significance, possesses again potential prospects for commercial application simultaneously.
In the regioselectivity and stereoselectivity control of polymkeric substance, uncontrollable compared to the selectivity of anionoid polymerization, polycoordination has obviously advantage.Coordination catalyst more such as based on rare earth metal or transition metal has been in the news by styrene catalyzed-butadiene copolymer conjunction, styrene-isoprene copolymerization, can obtain highly have rule polymkeric substance, but there is the multipolymer but very difficult acquisition of normality vinylbenzene segment between height, therefore being had by coordination polymerization process synthesis highly has the multipolymer of the vinylbenzene segment of rule all to have challenge in academia and industry member so far, but is again extremely promising simultaneously.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the preparation method providing a kind of constraint geometrical rear-earth title complex and preparation method thereof, polymerization catalyst system and preparation method thereof, polymkeric substance.
In order to solve above technical problem, the invention provides a kind of rare earth compounding, general formula is
Formula I
R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl;
R 2be selected from methylene radical, ethyl or dimethyl silica-based;
R 3be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 4be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 5be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl;
Ln is selected from Lu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Sc;
X is selected from CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2.
Preferably, be any one in following complex 1 ~ 36: complex 1:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=CH 2SiMe 3; Complex 2:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=CH 2SiMe 3; Complex 3:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Nd, X=CH 2SiMe 3; Complex 4:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Gd, X=CH 2SiMe 3; Complex 5:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=CH 2SiMe 3; Complex 6:R 1=C 5H 4, R 2= iPr, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=CH 2SiMe 3; Complex 7:R 1=C 5H 4, R 2= iPr, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=CH 2SiMe 3; Complex 8:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=Me, Ln=Sc, X=CH 2SiMe 3; Complex 9:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=Me, Ln=Lu, X=CH 2SiMe 3; Complex 10:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=Me, Ln=Y, X=CH 2SiMe 3; Complex 11:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( iPr) 3C 6H 2, Ln=Lu, X=CH 2SiMe 3; Complex 12:R 1=C 9H 6, R 2=CH 2, R 3=H,R 4=H, R 5=H, R 6=H, Ln=Sc, X=CH 2SiMe 3; Complex 13:R 1=C 9H 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=CH 2SiMe 3; Complex 14:R 1=C 9H 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=CH 2SiMe 3; Complex 15:R 1=C 9H 6, R 2=CH 2, R 3=H,R 4=H, R 5=H, R 6=2,4,6-( iPr) 3C 6H 2, Ln=Lu, X=CH 2SiMe 3; Complex 16:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=CH 2SiMe 3; Complex 17:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=CH 2SiMe 3; Complex 18:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=CH 2SiMe 3; Complex 19:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=CH 2SiMe 3; Complex 20:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc,X=o-NMe 2-CH 2C 6H 4; Complex 21:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=o-NMe 2-CH 2C 6H 4; Complex 22:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Nd, X=o-NMe 2-CH 2C 6H 4; Complex 23:R 1=C 5H 4,R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Gd, X=o-NMe 2-CH 2C 6H 4; Complex 24:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=o-NMe 2-CH 2C 6H 4; Complex 25:R 1=C 5H 4, R 2= iPr, R 3=H, R 4=H, R 5=H, R 6=Me, Ln=Lu, X=o-NMe 2-CH 2C 6H 4; Complex 26:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=Me, Ln=Sc, X=o-NMe 2-CH 2C 6H 4; Complex 27:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=2,6-(Me) 2C 6H 3, Ln=Sc, X=o-NMe 2-CH 2C 6H 4; Complex 28:R 1=C 5H 4, R 2= tBu, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=o-NMe 2-CH 2C 6H 4; Complex 29:R 1=C 9H 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=o-NMe 2-CH 2C 6H 4; Complex 30:R 1=C 9H 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=o-NMe 2-CH 2C 6H 4; Complex 31:R 1=C 9H 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=o-NMe 2-CH 2C 6H 4; Complex 32:R 1=C 9H 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=o-NMe 2-CH 2C 6H 4; Complex 33:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=o-NMe 2-CH 2C 6H 4; Complex 34:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=o-NMe 2-CH 2C 6H 4; Complex 35:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=o-NMe 2-CH 2C 6H 4; Complex 36:R 1=C 13H 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=o-NMe 2-CH 2C 6H 4.
The present invention also provides a kind of preparation method of rare earth compounding, comprises the following steps:
At N 2under protection, by constrained geometry configuration part R 1h-R 2-(3-R 3-4-R 4-5-R 5-6-R 6) C 5n is dissolved in tetrahydrofuran (THF) at-78 DEG C ~ 0 DEG C, adds normal hexane solution that concentration is the n-Butyl Lithium of 1.0 ~ 2.0mol/L successively, chemical formula is LnCl 3(thf) nthe rare earth trichloride of (n=2 ~ 3.5) and single anion ligand, described single anion ligand is CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2; R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl; R 2be selected from methylene radical, ethyl or dimethyl silica-based; R 3be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 4be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 5be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Ln is selected from Lu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Sc.
Preferably, the mol ratio of described constrained geometry configuration part, n-Butyl Lithium, rare earth trichloride and single anion ligand is 1: 1: 1: 2.
The present invention also provides a kind of polymerization catalyst system, by the rare earth compounding described in technique scheme, organic boron salt and alkylating reagent in molar ratio 1: (1 ~ 2): (2 ~ 1000) form.
Preferably, described organic boron salt is [Ph 3c] [B (C 6f 5) 4], [PhNMe 2h] [BPh 4], [PhNMe 2h] [B (C 6f 5) 4] or B (C 6f 5) 3.
Preferably, described alkylating reagent is molecular formula is AlR 3aluminum alkyls, molecular formula be HAlR 2alkyl-al hydride, molecular formula be AlR 2the alkyl aluminum chloride of Cl or aikyiaiurnirsoxan beta.
Preferably, described aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium or diethylbenzyl aluminium;
Described alkyl-al hydride is dimethyl hydrogenated aluminium, ADEH, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride or ethyl p-methylphenyl aluminum hydride;
Described alkyl aluminum chloride is dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-n-butyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, phenylbenzene aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, Ethylbenzyl chlorination aluminium or ethyl p-methylphenyl aluminum chloride;
Described aikyiaiurnirsoxan beta is methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta or normal-butyl aikyiaiurnirsoxan beta.
The present invention also provides a kind of preparation method be polymerized with catalyst system, comprises the following steps:
By the rare earth compounding described in technique scheme, organic boron salt and alkylating reagent in molar ratio 1: (1 ~ 2): (2 ~ 1000) are at C 6~ C 7aromatic hydrocarbon solvent in mix, obtain polymerization catalyst system.
The present invention also provides a kind of preparation method of polystyrene, comprises the following steps:
Styrene monomer is added in the organic solution of the polymerization catalyst system described in technique scheme, the mol ratio of described styrene monomer and described rare earth compounding is (250 ~ 4000): 1, polyreaction 1 ~ 30 minute at-20 ~ 80 DEG C, add ethanol solution hydrochloride and stop polyreaction, after sedimentation, drying, obtain polystyrene.
The present invention also provides a kind of preparation method of multipolymer, comprises the following steps:
Reaction monomers is added in the organic solution of the rare earth compounding described in technique scheme, described reaction monomers is the mix monomer of divinyl and cinnamic mix monomer or vinylbenzene and isoprene, the mol ratio of described reaction monomers and described rare earth compounding is (250 ~ 2000): 1, polyreaction 5 ~ 60 minutes at-20 ~ 80 DEG C, add ethanol solution hydrochloride and stop polyreaction, after sedimentation, drying, obtain polymkeric substance.
The invention provides a kind of rare earth compounding and preparation method thereof, the method synthesis is simple, and yield is up to 45% ~ 67%.The present invention also provides a kind of polymerization catalyst system and preparation method thereof, and this catalyst system is by above-mentioned rare earth compounding, organic boron salt and alkylating reagent in molar ratio 1: (1 ~ 2): (2 ~ 1000) form.Compared with prior art, the styrene catalyzed syndiotactic polymerization reaction of this polymerization catalyst system has the feature of controllable polymerization.In addition, the present invention also provides a kind of preparation method of polystyrene, and when utilizing above-mentioned polymerization catalyst system polymerizing styrene catalyzed, monomer conversion reaches as high as 100%, and activity reaches as high as 1.25 × 10 7g mol ln -1h -1, between synthesized polystyrene, normality (rrrr) reaches as high as 100%, and fusing point is within the scope of 266 ~ 272 DEG C, and number-average molecular weight is in 4.6 ~ 1,000,000 scopes, and molecular weight distribution is minimum reaches 1.20.Simultaneously, utilize this polymerization catalyst system Butadiene and cinnamic copolymerization, the composition obtaining each monomeric unit in multipolymer can be controlled by the feed molar ratio of monomer, and prepared copolymer characteristic is polystyrene segment is isostructure, reaches 100%; Polybutadiene segments is mainly along Isosorbide-5-Nitrae-structure, can reach 99.3%; Utilize the styrene catalyzed polyisoprene segments obtained with the polyreaction of isoprene of this polymerization catalyst system to be mainly 3,4-structure, can 73.5% be reached.
Embodiment
The invention discloses a kind of rare earth compounding, general formula is
Formula I
R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is the substituting group on the substituting group on fluorenyl, the substituting group on indenyl or cyclopentadienyl, and A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl; R 2for bridging substituting group, be selected from methylene radical, ethyl or dimethyl silica-based; R 3for the substituting group on skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 4for the substituting group on skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 5for the substituting group on skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 6for the substituting group on skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Ln represents rare earth metal, is selected from Lu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Sc; X is single anion ligand, is selected from CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2.
Concrete, this rare earth compounding is any one in title complex 1 ~ 36, and wherein, title complex 1-19 is rare earth alkyl complexes, and title complex 20-36 is rare earth benzyl title complex.
Accordingly, the present invention also provides a kind of preparation method of rare earth compounding, comprises the following steps: at N 2under protection, by constrained geometry configuration part R 1h-R 2-(3-R 3-4-R 4-5-R 5-6-R 6) C 5n is dissolved in tetrahydrofuran (THF) at-78 DEG C ~ 0 DEG C, adds normal hexane solution that concentration is the n-Butyl Lithium of 1.0 ~ 2.0mol/L successively, chemical formula is LnCl 3(thf) nthe rare earth trichloride of (n=2 ~ 3.5) and single anion ligand, described single anion ligand is CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2; R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl; R 2be selected from methylene radical or ethyl or dimethyl silica-based; R 3be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 4be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 5be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Ln is selected from Lu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Sc.As preferably, the mol ratio of described constrained geometry configuration part, n-Butyl Lithium, rare earth trichloride and single anion ligand is preferably 1: 1: 1: 2.
As preferably, the preparation process of described rare earth compounding is specially: N 2under protection, constrained geometry configuration part is dissolved in tetrahydrofuran (THF) at-78 DEG C ~ 0 DEG C, adds normal hexane solution that concentration is the n-Butyl Lithium of 1.0 ~ 2.0mol/L, to add chemical formula after 1 hour be LnCl in reaction 3(thf) nthe rare earth trichloride of (n=2 ~ 3.5), react and add single anion ligand after 4 hours, described single anion ligand is CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2; Room temperature reaction is after 4 hours, and except desolventizing, with hexane extraction, concentrated hexane obtains constraint geometrical rear-earth alkyl complexes; R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl; R 2be selected from methylene radical or ethyl or dimethyl silica-based; R 3be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 4be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 5be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Ln is selected from Lu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Sc.
Take single anion ligand as CH 2siMe 3for example, the synthetic route of constraint geometrical rear-earth alkyl complexes is as follows:
Condition and step as follows: N 2under protection, constrained geometry configuration part R 1h-R 2-(3-R 3-4-R 4-5-R 5-6-R 6) C 5n is dissolved in tetrahydrofuran (THF) and is placed in-78 ~ 0 DEG C, the concentration adding 1 times amount of the mol of described constrained geometry configuration part is the normal hexane solution of 1.0 ~ 2.0mol/L n-Butyl Lithium, react after 1 hour, add the rare earth trichloride of 1 times amount of the mol of described constrained geometry configuration part, react after 4 hours, add the LiCH of 2 times amount of the mol of described constrained geometry configuration part 2siMe 3, room temperature reaction is after 4 hours, and except desolventizing, with hexane extraction, concentrated hexane, obtains constraint geometrical rear-earth alkyl complexes; The chemical formula of described rare earth trichloride is LnCl 3(thf) 3, wherein Ln is identical with the Ln in formula I.
In addition, take single anion ligand as o-NMe 2-CH 2c 6h 4for example, the synthetic route of constraint geometrical rear-earth alkyl complexes is as follows:
Condition and step as follows: N 2under protection, constrained geometry configuration part R 1h-R 2-(3-R 3-4-R 4-5-R 5-6-R 6) C 5n is dissolved in tetrahydrofuran (THF) and is placed in-78 ~ 0 DEG C, the concentration adding 1 times amount of the mol of described constrained geometry configuration part is the normal hexane solution of 1.0 ~ 2.0mol/L n-Butyl Lithium, react after 1 hour, add the rare earth trichloride of 1 times amount of the mol of described constrained geometry configuration part, react after 4 hours, add the LiCH of 2 times amount of the mol of described constrained geometry configuration part 2c 6h 4nMe 2-o, room temperature reaction is after 12 hours, and except desolventizing, with toluene extraction, concentrated toluene, obtains constraint geometrical rear-earth Bian Ji title complex; The chemical formula of described rare earth chloride is LnCl 3(thf) n(n=2 ~ 3.5), the Ln wherein in Ln cotype I.
The present invention also aims to provide a kind of polymerization catalyst system, by the rare earth compounding described in technique scheme, organic boron salt and alkylating reagent in molar ratio 1: (1 ~ 2): (2 ~ 1000) form.Wherein, described organic boron salt is preferably [Ph 3c] [B (C 6f 5) 4], [PhNMe 2h] [BPh 4], [PhNMe 2h] [B (C 6f 5) 4] or B (C 6f 5) 3; It is AlR that described alkylating reagent is preferably molecular formula 3aluminum alkyls, molecular formula be HAlR 2alkyl-al hydride, molecular formula be AlR 2the alkyl aluminum chloride of Cl or aikyiaiurnirsoxan beta.Preferred, described aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium or diethylbenzyl aluminium; Described alkyl-al hydride is dimethyl hydrogenated aluminium, ADEH, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride or ethyl p-methylphenyl aluminum hydride; Described alkyl aluminum chloride is dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-n-butyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, phenylbenzene aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, Ethylbenzyl chlorination aluminium or ethyl p-methylphenyl aluminum chloride; Described aikyiaiurnirsoxan beta is methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta or normal-butyl aikyiaiurnirsoxan beta.
Above-mentioned polymerization catalyst system is prepared as follows, and comprises the following steps: by the rare earth compounding described in such scheme, organic boron salt and alkylating reagent in molar ratio 1: (1 ~ 2): (2 ~ 1000) are at C 6~ C 7aromatic hydrocarbon solvent in mix, obtain polymerization catalyst system.In above-mentioned polymerization catalyst system preparation process, this cation compound and monomer coordination are inserted, and obtain macromolecular chain, and alkylating reagent has removal of impurities effect, for eliminating the impurity of catalytic process.The mol ratio of rare earth compounding, organic boron salt and alkylating reagent affects the katalysis of this catalyst system, and alkylating reagent mol ratio is excessive, and macromolecular chain can be caused to shift, affect polymerization effect, alkylating reagent mol ratio is too small, impurity-eliminating effect may be caused not good, affect catalytic efficiency.In addition, organic boron salt and rare earth compounding preferably feed intake by 1: 1 or 2: 1, generate cationic effect to reach.
Accordingly, the present invention also provides the application of the rare earth compounding described in a kind of technique scheme in syndiotactic polymerization of phenylethylene, and the application of the rare earth compounding described in a kind of technique scheme in vinylbenzene and isoprene copolymer close is provided, and the application of rare earth compounding in vinylbenzene and butadiene copolymer close described in technique scheme.The invention provides a kind of preparation method of polystyrene, comprise the following steps: in the organic solution of the polymerization catalyst system described in such scheme, add styrene monomer, the mol ratio of described styrene monomer and described rare earth compounding is (250 ~ 4000): 1, polyreaction 1 ~ 30 minute at-20 ~ 80 DEG C, add ethanol solution hydrochloride and stop polyreaction, after sedimentation, drying, obtain polystyrene.Wherein, described organic solvent is preferably toluene or chlorobenzene, and described organic solvent is (100 ~ 1000) L: 1mol with the Molar ratio of described rare earth compounding; The concentration of described ethanol solution hydrochloride is 10%.In addition, the present invention also provides a kind of preparation method of multipolymer, comprise the following steps: in the organic solution of the rare earth compounding described in such scheme, add reaction monomers, described reaction monomers is the mix monomer of divinyl and cinnamic mix monomer or vinylbenzene and isoprene, the mol ratio of described reaction monomers and described rare earth compounding is (250 ~ 2000): 1, polyreaction 5 ~ 60 minutes at-20 ~ 80 DEG C, add ethanol solution hydrochloride and stop polyreaction, after sedimentation, drying, obtain polymkeric substance.Wherein, described organic solvent is preferably pentane, hexane, toluene or chlorobenzene, and described organic solvent is (500 ~ 5000) L: 1mol with the Molar ratio of described rare earth compounding; The concentration of described ethanol solution hydrochloride is 10%.
The number-average molecular weight of the syndiotactic polystyrene of above-mentioned gained and isoprene styrene or butadiene-styrene copolymer and molecular weight distribution high-temperature gel permeation chromatography instrument (GPC) measure, fusing point DSC measures, between polystyrene normality (rrrr) with proton nmr spectra ( 1h NMR) and carbon spectrum ( 13c NMR) wave spectrum calculate, polymer chain segment unit with proton nmr spectra ( 1h NMR) wave spectrum calculating.
The constraint geometrical rear-earth title complex synthetic method provided of the present invention is simple, and yield is comparatively up to 45% ~ 67%.The styrene catalyzed syndiotactic polymerization of catalyst system that this rare earth compounding and organic boron salt and alkylating reagent form reacts the feature with controllable polymerization, can realize vinylbenzene and all be polymerized, styrene-isoprene copolymerization, and styrene butadiene copolymers closes.First this system can obtain the syndiotactic polystyrene of > 99%, and the activity of this system reaches 1.56 × 10 again 7g/mol ln.h, reach industrial standard completely, this system of what is more important can realize vinylbenzene and conjugated alkene as 1.3-divinyl, and the copolymerization of isoprene, solves the application limitation of syndiotactic polystyrene.
In order to further illustrate technical scheme of the present invention, be described below in conjunction with embodiment.
The chemical reagent that the embodiment of the present invention adopts is commercial.
The preparation of embodiment 1 title complex 1
Under-40 DEG C of conditions, be the hexane solution (1.2mL of the n-Butyl Lithium of 1.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-(2-the pyridyl)-tertiary butyl-cyclopentadiene (0.24g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains red crystals title complex 1 0.26g altogether, productive rate 54%.Ultimate analysis target molecule formula is C 26h 46nOSi 2sc (%): C, 63.75; H, 9.47; N, 2.86.
The preparation of embodiment 2 ~ 5 title complex 2-5
Change reactant rare earth trichloride, other condition and step with complex preparation embodiment 1, the constraint geometrical rear-earth alkyl complexes 2-5 obtained and result as shown in table 1:
Constraint geometrical rear-earth alkyl complexes 2-5 prepared by table 1 embodiment 2 ~ 5
Title complex Rare earth trichloride Target molecule formula Ultimate analysis (%) Productive rate (%)
2 YCl 3(thf) 3.5 C 26H 46NSi 2Y C，58.51；H，8.68；N，2.62 48
3 NdCl 3(thf) 2 C 26H 46NSi 2Nd C，53.01；H，7.87；N，2.37 45
4 GdCl 3(thf) 3 C 26H 46NSi 2Gd C，51.86；H，7.70；N，2.33 63
5 LuCl 3(thf) 3 C 26H 46NSi 2Lu C，50.38；H，7.48；N，2.26 61
The preparation of embodiment 6 title complex 6
Under-78 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-[2-pyridyl]-sec.-propyl-cyclopentadiene (0.22g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains reddish crystals title complex 6 0.28g altogether, productive rate 58%.Ultimate analysis target molecule formula is C 25h 44nSi 2sc (%): C, 63.11; H, 9.32; N, 2.94.
The preparation of embodiment 7 title complex 7
Under-78 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-[2-pyridyl]-sec.-propyl-cyclopentadiene (0.22g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains reddish crystals title complex 7 0.41g altogether, productive rate 61%.Ultimate analysis target molecule formula is C 25h 44nSi 2lu (%): C, 49.57; H, 7.32; N, 2.31.
The preparation of embodiment 8 title complex 8
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-[2-(6-methyl) the pyridyl]-tertiary butyl-cyclopentadiene (0.25g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains reddish crystals title complex 8 0.25g altogether, productive rate 48%.Ultimate analysis target molecule formula is C 26h 48nSi 2sc (%): C, 49.48; H, 7.38; N, 2.31.
The preparation of embodiment 9 ~ 10 title complex 9 ~ 10
In the preparation method of title complex 9-10, change reactant rare earth trichloride, the constraint geometrical rear-earth alkyl complexes 9-10 that other condition and step obtain with complex preparation embodiment 8 and result are as table 2:
Constraint geometrical rear-earth alkyl complexes 9-10 prepared by table 2 embodiment 9 ~ 10
Title complex Rare earth trichloride Target molecule formula Ultimate analysis (%) Productive rate (%)
9 LuCl 3(thf) 3 C 26H 48NSi 2Lu C，49.51；H，7.30；N，2.30 48
10 YCl 3(thf) 3.5 C 26H 48NSi 2Y C，58.25；H，9.01；N，2.61 45
The preparation of embodiment 11 title complex 11
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise to 1-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl-tertiary butyl-cyclopentadiene (0.48g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains reddish crystals title complex 11 0.36g altogether, productive rate 46%.Ultimate analysis target molecule formula is C 39h 67nSi 2lu (%): C, 59.97; H, 8.62; N, 1.78.
The preparation of embodiment 12 title complex 12
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 3-(2-pyridyl)-methylene radical-indenes (0.23g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains reddish crystals title complex 12 0.21g altogether, productive rate 42%.Ultimate analysis target molecule formula is C 28h 44nOSi 2sc (%): C, 65.72; H, 8.65; N, 2.73.
The preparation of embodiment 13 title complex 13
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 3-(2-pyridyl)-methylene radical-indenes (0.23g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 13 0.26g altogether, productive rate 53%.Ultimate analysis target molecule formula is C 28h 44nOSi 2lu (%): C, 51.98; H, 6.90; N, 2.15.
Prepared by embodiment 14 title complex 14
Under-20 DEG C of conditions, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 3-(2-pyridyl)-methylene radical-indenes (0.23g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by YCl 3(thf) 3.5(0.54g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 14 0.26g altogether, productive rate 53%.Ultimate analysis target molecule formula is C 28h 44nOSi 2y (%): C, 60.50; H, 7.98; N, 2.52.
The preparation of embodiment 15 title complex 15
Under-78 DEG C of conditions, be the hexane solution (1.2mL of the n-Butyl Lithium of 1.0mol/L by concentration, 1.2mmol) be added drop-wise to 3-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl-methylene radical-indenes (0.49g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 15 0.25g altogether, productive rate 64%.Ultimate analysis target molecule formula is C 39h 59n Si 2lu (%): C, 60.12; H, 6.34; N, 1.78.
The preparation of embodiment 16 title complex 16
Under-78 DEG C of conditions, be the hexane solution (1.2mL of the n-Butyl Lithium of 1.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 9-(2-pyridyl)-methylene radical-fluorenes (0.30g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 16 0.26g altogether, productive rate 58%.Ultimate analysis target molecule formula is C 32h 49scNOSi 2(%): C, 68.01; H, 8.70; N, 2.45.
The preparation of embodiment 17 title complex 17
Under-40 DEG C of conditions, be the hexane solution (1.2mL of the n-Butyl Lithium of 1.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 9-(2-pyridyl)-methylene radical-fluorenes (0.30g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 17 0.28g altogether, productive rate 55%.Ultimate analysis target molecule formula is C 32h 49luNOSi 2(%): C, 55.31; H, 7.05; N, 2.00.
The preparation of embodiment 18 title complex 18
Under-20 DEG C of conditions, be the hexane solution (1.2mL of the n-Butyl Lithium of 1.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 9-(2-pyridyl)-methylene radical-fluorenes (0.30g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by YCl 3(thf) 3.5(0.54g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 18 0.37g altogether, productive rate 61%.Ultimate analysis target molecule formula is C 32h 49yNOSi 2(%): C, 63.12; H, 8.05; N, 2.30.
The preparation of embodiment 19 title complex 19
Under-20 DEG C of conditions, be the hexane solution (1.2mL of the n-Butyl Lithium of 1.0mol/L by concentration, 1.2mmol) be added drop-wise to 9-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl-methylene radical-fluorenes (0.55g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2siMe 3(0.23g, 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum pumps solvent, resistates hexane extraction, and concentrated hexane solution obtains scarlet crystal title complex 19 0.47g altogether, productive rate 61%.Ultimate analysis target molecule formula is C 47h 68scNOSi 2(%): C, 73.82; H, 8.95; N, 1.83.
The preparation of embodiment 20 title complex 20
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-(2-the pyridyl)-tertiary butyl-cyclopentadiene (0.24g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains reddish yellow crystal title complex 20 0.30g altogether, productive rate 53%.Ultimate analysis target molecule formula is C 35h 49n 3sc (%): C, 74.11; H, 8.87; N, 7.52.
The preparation of embodiment 21 ~ 24 title complex 21-24
In the preparation method of title complex 21-24, change reactant rare earth trichloride, other condition and step are with complex preparation embodiment 20, and the constraint geometrical rear-earth alkyl complexes 21-24 obtained and result are as table 3:
Constraint geometrical rear-earth alkyl complexes 21 ~ 24 prepared by table 3 embodiment 21 ~ 24
Title complex Rare earth trichloride Target molecule formula Ultimate analysis (%) Productive rate (%)
21 YCl 3(thf) 3.5 C 35H 49N 3Y C，69.51；H，8.20；N，6.90 48
22 NdCl 3(thf) 2 C 35H 49N 3Nd C，64.05；H，7.51；N，6.41 45
23 GaCl 3(thf) 3 C 35H 49N 3Ga C，72.25；H，8.45；N，7.22 50
24 LuCl 3(thf) 3 C 35H 49N 3Lu C，61.21；H，7.16；N，6.12 53
The preparation of embodiment 15 title complex 25
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-(2-pyridyl)-sec.-propyl-cyclopentadiene (0.22g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains reddish yellow crystal title complex 25 0.20g altogether, productive rate 48%.Ultimate analysis target molecule formula is C 21h 28nSc (%): C, 74.01; H, 8.25; N, 3.98.
The preparation of embodiment 26 title complex 26
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 1-[2-(6-methyl) the pyridyl]-tertiary butyl-cyclopentadiene (0.26g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains reddish yellow crystal title complex 26 0.23g altogether, productive rate 41%.Ultimate analysis target molecule formula is C 36h 51n 3sc (%): C, 53.45; H, 5.94; N, 2.85.
The preparation of embodiment 27 title complex 27
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise to 1-[2-(2,6-3,5-dimethylphenyl) pyridyl]-the tertiary butyl-cyclopentadiene (0.33g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains reddish yellow crystal title complex 27 0.21g altogether, productive rate 44%.Ultimate analysis target molecule formula is C 43h 57n 3sc (%): C, 77.48; H, 7.40; N, 3.38.
The preparation of embodiment 28 title complex 28
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise to 1-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl-tertiary butyl-cyclopentadiene (0.36g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol)) be added in above-mentioned reaction solution, react after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains reddish yellow crystal title complex 28 0.25g altogether, productive rate 48%.Ultimate analysis target molecule formula is C 50h 71n 3sc (%): C, 78.00; H, 7.88; N, 3.16.
The preparation of embodiment 29 title complex 29
Under-40 DEG C of conditions, be the hexane solution (0.8mL of the n-Butyl Lithium of 1.5mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 3-(2-pyridyl)-methylene radical-indenes (0.23g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains reddish yellow crystal title complex 29 0.30g altogether, productive rate 48%.Ultimate analysis target molecule formula is C 37h 48n 3lu (%): C, 79.48; H, 7.03; N, 2.54.
The preparation of embodiment 30 title complex 30
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 3-(2-pyridyl)-methylene radical-indenes (0.23g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 30 0.16g altogether, productive rate 43%.Ultimate analysis target molecule formula is C 37h 48n 3sc (%): C, 75.00; H, 6.21; N, 4.32.
The preparation of embodiment 31 title complex 31
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 3-(2-pyridyl)-methylene radical-indenes (0.23g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by YCl 3(thf) 3.5(0.54g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 31 0.30g altogether, productive rate 56%.Ultimate analysis target molecule formula is C 37h 48n 3y (%): C, 53.34; H, 4.39; N, 3.04.
The preparation of embodiment 32 title complex 32
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise to 3-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl-methylene radical-indenes (0.48g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 32 0.44g altogether, productive rate 56%.Ultimate analysis target molecule formula is C 52h 72n 3sc (%): C, 79.65; H, 9.25; N, 5.34.
The preparation of embodiment 33 title complex 33
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 9-(2-pyridyl)-methylene radical-fluorenes (0.30g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 33 0.29g altogether, productive rate 50%.Ultimate analysis target molecule formula is C 38h 44n 3sc (%): C, 77.65; H, 7.54; N, 7.14.
The preparation of embodiment 34 title complex 34
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 9-(2-pyridyl)-methylene radical-fluorenes (0.30g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by YCl 3(thf) 3.5(0.54g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 34 0.32g altogether, productive rate 50%.Ultimate analysis target molecule formula is C 38h 44n 3y (%): C, 72.24; H, 7.01; N, 6.61.
The preparation of embodiment 35 title complex 35
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise in the solution of the tetrahydrofuran (THF) (20mL) of 9-(2-pyridyl)-methylene radical-fluorenes (0.30g, 1.2mmol).Reaction solution reacts after 1 hour at this temperature by LuCl 3(thf) 3(0.59g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 35 0.36g altogether, productive rate 50%.Ultimate analysis target molecule formula is C 38h 44n 3lu (%): C, 63.45; H, 6.15; N, 5.84.
The preparation of embodiment 36 title complex 36
Under 0 DEG C of condition, be the hexane solution (0.6mL of the n-Butyl Lithium of 2.0mol/L by concentration, 1.2mmol) be added drop-wise to 9-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl-methylene radical-fluorenes (0.55g, 1.2mmol) tetrahydrofuran (THF) (20mL) solution in.Reaction solution reacts after 1 hour at this temperature by ScCl 3(thf) 3(0.44g, 1.2mmol) is added in above-mentioned reaction solution, reacts after 4 hours, by LiCH 2c 6h 4nMe 2-o (0.34g, 2.4mmol) adds, and room temperature reaction is after 12 hours, and vacuum pumps solvent, and resistates toluene extracts, and concentrated toluene solution obtains yellow crystals title complex 36 0.42g altogether, productive rate 50%.Ultimate analysis target molecule formula is C 56h 73n 3sc (%): C, 80.72; H, 8.81; N, 5.03.
The preparation embodiment of catalyst system is as follows:
The preparation of embodiment 37 coordination catalyst system 1
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,10 μm of ol [Ph to 25ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 2000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 1.
The preparation of embodiment 38 coordination catalyst system 2
At-20 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,20 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and hexane solvent, the volume L of hexane solvent is 4000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 2.
The preparation of embodiment 39 coordination catalyst system 3
At 80 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,20 μm of ol [Ph to 100ml 3c] [B (C 6f 5) 4], the methylaluminoxane of 10000 μm of ol and xylene solvent, the volume L of xylene solvent is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 3.
The preparation of embodiment 40 coordination catalyst system 4
At 0 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the AlMe of 50 μm of ol 3, and pentane solvent, the volume L of pentane solvent is 2500: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 4.
The preparation of embodiment 41 coordination catalyst system 5
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,20 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the AlEt of 200 μm of ol 3, and hexane solvent, the volume L of hexane solvent is 3000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 5.
The preparation of embodiment 42 coordination catalyst system 6
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,10 μm of ol [Ph to 25ml 3c] [B (C 6f 5) 4], the HAl of 20 μm of ol ipr 2, and toluene solvant, the volume L of toluene solvant is 1500: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 6.
The preparation of embodiment 43 coordination catalyst system 7
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 1,10 μm of ol [Ph to 25ml 3c] [B (C 6f 5) 4], the Al of 200 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 2000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 1, reacts 2 minutes, obtains coordination catalyst system 7.
The preparation of embodiment 44 catalyst system 8
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 2,20 μm of ol [Ph to 25ml 3c] [B (C 6f 5) 4], the AlEt of 200 μm of ol 2cl and xylene solvent, the volume L of xylene solvent is 3500: 1 with the mol number ratio of constraint geometrical rear-earth title complex 2, reacts 2 minutes, obtains catalyst system 8.
The preparation of embodiment 45 coordination catalyst system 9
At 40 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 3,10 μm of ol [Ph to 25ml 3c] [B (C 6f 5) 4], the Al of 500 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 2000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 3, reacts 2 minutes, obtains coordination catalyst system 9.
The preparation of embodiment 46 coordination catalyst system 10
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 4,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 500 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 2000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 4, reacts 2 minutes, obtains coordination catalyst system 10.
The preparation of embodiment 47 coordination catalyst system 11
At 80 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 4,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 200 μm of ol ibu 3, and chlorobenzene solvent, the volume L of chlorobenzene solvent is 3000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 4, reacts 2 minutes, obtains coordination catalyst system 11.
The preparation of embodiment 48 coordination catalyst system 12
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 5,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 500: 1 with the mol number ratio of constraint geometrical rear-earth title complex 5, reacts 2 minutes, obtains coordination catalyst system 12.
The preparation of embodiment 49 coordination catalyst system 13
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 6,20 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the methylaluminoxane of 10000 μm of ol and xylene solvent, the volume L of xylene solvent is 3000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 6, reacts 2 minutes, obtains coordination catalyst system 13.
The preparation of embodiment 50 coordination catalyst system 14
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 7,10 μm of ol [Ph to 25ml 3c] [B (C 6f 5) 4], the Al of 200 μm of ol ibu 3, and pentane solvent, the volume L of pentane solvent is 2500: 1 with the mol number ratio of constraint geometrical rear-earth title complex 7, reacts 2 minutes, obtains coordination catalyst system 14.
The preparation of embodiment 51 coordination catalyst system 15
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 8,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 8, reacts 2 minutes, obtains coordination catalyst system 15.
The preparation of embodiment 52 coordination catalyst system 16
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 9,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 9, reacts 2 minutes, obtains coordination catalyst system 16.
The preparation of embodiment 53 coordination catalyst system 53
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 10,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 10, reacts 2 minutes, obtains coordination catalyst system 17.
The preparation of embodiment 54 coordination catalyst system 18
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 11,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 11, reacts 2 minutes, obtains coordination catalyst system 18.
The preparation of embodiment 55 coordination catalyst system 19
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 12,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 12, reacts 2 minutes, obtains coordination catalyst system 19.
The preparation of embodiment 56 coordination catalyst system 20
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 13,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 13, reacts 2 minutes, obtains coordination catalyst system 20.
The preparation of embodiment 57 coordination catalyst system 21
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 14,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 14, reacts 2 minutes, obtains coordination catalyst system 21.
The preparation of embodiment 58 coordination catalyst system 22
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 15,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 15, reacts 2 minutes, obtains coordination catalyst system 22.
The preparation of embodiment 59 coordination catalyst system 23
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 16,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 16, reacts 2 minutes, obtains coordination catalyst system 23.
The preparation of embodiment 60 coordination catalyst system 24
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 17,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 17, reacts 2 minutes, obtains coordination catalyst system 24.
The preparation of embodiment 61 coordination catalyst system 25
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 18,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 18, reacts 2 minutes, obtains coordination catalyst system 25.
The preparation of embodiment 62 coordination catalyst system 26
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 19,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 19, reacts 2 minutes, obtains coordination catalyst system 26.
The preparation of embodiment 63 coordination catalyst system 27
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 20,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 20, reacts 2 minutes, obtains coordination catalyst system 27.
The preparation of embodiment 64 coordination catalyst system 28
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 21,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 21, reacts 2 minutes, obtains coordination catalyst system 28.
The preparation of embodiment 65 coordination catalyst system 29
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 22,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 22, reacts 2 minutes, obtains coordination catalyst system 29.
The preparation of embodiment 66 coordination catalyst system 30
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 23,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 23, reacts 2 minutes, obtains coordination catalyst system 30.
The preparation of embodiment 67 coordination catalyst system 31
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 24,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 24, reacts 2 minutes, obtains coordination catalyst system 31.
The preparation of embodiment 68 coordination catalyst system 32
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 25,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 25, reacts 2 minutes, obtains coordination catalyst system 32.
The preparation of embodiment 69 coordination catalyst system 33
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 26,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 26, reacts 2 minutes, obtains coordination catalyst system 33.
The preparation of embodiment 70 coordination catalyst system 34
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 27,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 27, reacts 2 minutes, obtains coordination catalyst system 34.
The preparation of embodiment 71 coordination catalyst system 35
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 28,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 28, reacts 2 minutes, obtains coordination catalyst system 35.
The preparation of embodiment 72 coordination catalyst system 36
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 29,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 29, reacts 2 minutes, obtains coordination catalyst system 36.
The preparation of embodiment 73 coordination catalyst system 37
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 30,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 30, reacts 2 minutes, obtains coordination catalyst system 37.
The preparation of embodiment 74 coordination catalyst system 38
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 31,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 31, reacts 2 minutes, obtains coordination catalyst system 38.
The preparation of embodiment 75 coordination catalyst system 39
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 32,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 32, reacts 2 minutes, obtains coordination catalyst system 39.
The preparation of embodiment 76 coordination catalyst system 40
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 33,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 33, reacts 2 minutes, obtains coordination catalyst system 40.
The preparation of embodiment 77 coordination catalyst system 41
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 34,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 34, reacts 2 minutes, obtains coordination catalyst system 41.
The preparation of embodiment 78 coordination catalyst system 42
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 35,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 35, reacts 2 minutes, obtains coordination catalyst system 42.
The preparation of embodiment 79 coordination catalyst system 43
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add 10 μm of ol title complexs, 36,10 μm of ol [Ph to 50ml 3c] [B (C 6f 5) 4], the Al of 100 μm of ol ibu 3, and toluene solvant, the volume L of toluene solvant is 5000: 1 with the mol number ratio of constraint geometrical rear-earth title complex 36, reacts 2 minutes, obtains coordination catalyst system 43.
Aggregated application embodiment is as follows:
With the above-mentioned catalyst system prepared, add the styrene monomer of corresponding mol ratio.Polymerization bottle is placed in 25 DEG C of thermostatic baths, stirs lower reaction.Add the ethanolic soln termination polyreaction that 2ml volumetric concentration is 10% hydrochloric acid, reaction soln is poured into sedimentation in 100ml methyl alcohol, obtain polystyrene white solid powder, again this polystyrene white solid powder is placed in vacuum drying oven dry 48 hours, obtain dry polystyrene white solid powder, weigh.Calculate transformation efficiency 100%, calculating polymerization activity is, with the number-average molecular weight (M of high temperature GPC analysis polystyrene n), molecular weight distribution (M w/ M n), normality (rrrr) between nmr analysis polystyrene, DSC measures the fusing point (T of syndiotactic polystyrene m).
The condition preparing syndiotactic polystyrene of Application Example 80-122 and the result of gained as shown in table 4:
The application of the novel constraint geometrical rear-earth alkyl complexes of table 4 in vinylbenzene (St) syndiotactic polymerization
Can draw from aggregated application embodiment 80 ~ 122, above-mentioned constraint geometrical rear-earth title complex can realize cinnamic high reactivity (1.66 × 10 5g mol ln -1h -1~ 1.25 × 10 7g mol ln -1h -1), advise (80% ~ 100%) polymerization between height.Prepared polystyrene number-average molecular weight is in 4.6 ~ 1,000,000 scopes, and molecular weight distribution narrower (1.20 ~ 1.98), fusing point is within the scope of 266 ~ 272 DEG C.Catalyst system has higher adaptability to temperature, and in the polymerization temperatures range of-20 ~ 80 DEG C, between polystyrene, the most Gao Junke of normality (rrrr) reaches 100%.
Styrene-isoprene copolymerization embodiment:
Embodiment 123
Get the toluene solution 5ml of coordination catalyst system 1, be placed in through polymerization bottle that is anhydrous, anaerobic process, add 1mmol styrene monomer and 1mmol isoprene monomer, polyreaction carries out 10 minutes at 25 DEG C simultaneously.Add the ethanolic soln termination polyreaction that 2ml volumetric concentration is 10% hydrochloric acid, reaction soln is poured into sedimentation in 100ml methyl alcohol, obtain styrene-isoprene random copolymers, again this multipolymer is placed in vacuum drying oven dry 48 hours, obtain the styrene-isoprene random copolymers of dry constant weight, net weight is respectively 0.15g.Transformation efficiency is respectively 90%.Calculating polymerization activity is 122kg (mol sch) -1, with nucleus magnetic hydrogen spectrum ( 1h NMR) analyze that to obtain cinnamic content in styrene-isoprene random copolymers be 14.3mol%, the content of isoprene is 85.7mol%, with the quantitative carbon spectrum of nuclear-magnetism ( 13c NMR) to analyze 3,4 content in the polyisoprene segments obtaining in styrene-isoprene random copolymers be 45.3%; Number-average molecular weight (the M of styrene-isoprene random copolymers is obtained with high temperature GPC analysis n) be 3.6 ten thousand, molecular weight distribution (M w/ M n) be 1.42, the fusing point (T of styrene-isoprene random copolymers is obtained with dsc analysis m) be 248 DEG C.
Embodiment 124 ~ 173
Embodiment 124 ~ 173 is the described embodiment of constraint geometrical rear-earth title complex in styrene-isoprene random copolymerization.Its step with embodiment 123, concrete condition and the result of gained as shown in table 5:
Table 5 coordination polymerization process synthesizing styrene-isoprene random copolymers
Can draw from the aggregated data of embodiment 123 ~ 174: the present invention passes through coordination polymerization process, adopt one kettle way (namely vinylbenzene and isoprene join in coordination catalyst system simultaneously), the coordination catalyst system that the catalyst system be made up of constraint geometrical rear-earth title complex and organic boron salt and aluminum alkyls forms is styrene catalyzed-and isoprene random copolymerization is when reacting, vinylbenzene is to reach as high as 92% with isoprene monomer total conversion rate, and activity reaches as high as 544kg (mol lnh) -1.In the styrene-isoprene random copolymers of preparation, cinnamic content is within the scope of 14.2 ~ 71.6mol%, shows that the content of monomer in styrene-isoprene random copolymers can regulate arbitrarily.The fusing point of the styrene-isoprene random copolymers of preparation reaches as high as 251 DEG C, and number-average molecular weight is in 3.6 ~ 110.5 ten thousand scopes, and molecular weight distribution is 1.19 ~ 1.94.
Styrene butadiene dualistic polymerization embodiment:
Embodiment 175
The toluene solution 5ml getting coordination catalyst system 1 is placed in through polymerization bottle that is anhydrous, anaerobic process, and add 1mmol styrene monomer and 1mmol divinylic monomer, polyreaction carries out 10 minutes at 25 DEG C simultaneously.Add the ethanolic soln termination polyreaction that 2ml volumetric concentration is 10% hydrochloric acid, reaction soln is poured into sedimentation in 100ml methyl alcohol, obtain styrene-butadiene block copolymer, again this multipolymer is placed in vacuum drying oven dry 48 hours, obtain the styrene-butadiene copolymer of dry constant weight, net weight is 0.14g.Transformation efficiency is respectively 92%.Calculating polymerization activity is 122kg (molSch) -1, with nucleus magnetic hydrogen spectrum ( 1h NMR) analyze that to obtain cinnamic content in styrene-butadiene block copolymer be 84.13mol%; With nuclear-magnetism quantitative carbon spectrum ( 13c NMR) to analyze cis Isosorbide-5-Nitrae content in the polybutadiene segments obtaining in styrene-butadiene block copolymer be 96.45%, obtains the number-average molecular weight (M of styrene butadiene block copolymer with high temperature GPC analysis n) be 3.6 ten thousand, molecular weight distribution (M w/ M n) be 1.42, the fusing point (T of styrene-butadiene block copolymer is obtained with dsc analysis m) be 248 DEG C.
Table 6 coordination polymerization process synthesizing styrene-butadiene block copolymer
Can draw from the aggregated data of embodiment 175 ~ 224: the coordination catalyst system that the catalyst system that constraint geometrical rear-earth title complex forms with organic boron salt and aluminum alkyls forms is styrene catalyzed-and butadiene block copolymer is when closing and react, vinylbenzene is to reach as high as 92% with divinylic monomer total conversion rate, and activity reaches as high as 514kg (mol lnh) -1.In the styrene butadiene random copolymer of preparation, cinnamic content is within the scope of 14.2 ~ 85.1mol%, shows that the content of monomer in styrene butadiene random copolymer can regulate arbitrarily.The fusing point of the styrene butadiene random copolymer of preparation reaches as high as 251 DEG C, and number-average molecular weight is in 3.6 ~ 109.5 ten thousand scopes, and molecular weight distribution is 1.34 ~ 1.94.

Claims (12)

1. a rare earth compounding, general formula is
R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is selected from hydrogen;
R 2be selected from methylene radical, ethylidene or dimethyl silica-based;
R 3be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 4be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 5be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl;
Ln is selected from Lu, Y or Sc;
X is selected from CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2.
2. rare earth compounding according to claim 1, is characterized in that, is any one in following title complex 12 ~ 19 and title complex 29 ~ 36:
Title complex 12:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=CH 2siMe 3;
Title complex 13:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=CH 2siMe 3;
Title complex 14:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=CH 2siMe 3;
Title complex 15:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( ipr) 3c 6h 2, Ln=Lu, X=CH 2siMe 3;
Title complex 16:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=CH 2siMe 3;
Title complex 17:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=CH 2siMe 3;
Title complex 18:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=CH 2siMe 3;
Title complex 19:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( ipr) 3c 6h 2, Ln=Sc, X=CH 2siMe 3;
Title complex 29:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=o-NMe 2-CH 2c 6h 4;
Title complex 30:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=o-NMe 2-CH 2c 6h 4;
Title complex 31:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=o-NMe 2-CH 2c 6h 4;
Title complex 32:R 1=C 9h 6, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( ipr) 3c 6h 2, Ln=Sc, X=o-NMe 2-CH 2c 6h 4;
Title complex 33:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Sc, X=o-NMe 2-CH 2c 6h 4;
Title complex 34:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Y, X=o-NMe 2-CH 2c 6h 4;
Title complex 35:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=H, Ln=Lu, X=o-NMe 2-CH 2c 6h 4;
Title complex 36:R 1=C 13h 8, R 2=CH 2, R 3=H, R 4=H, R 5=H, R 6=2,4,6-( ipr) 3c 6h 2, Ln=Sc, X=o-NMe 2-CH 2c 6h 4.
3. a preparation method for the rare earth compounding shown in formula I, comprises the following steps:
At N 2under protection, by constrained geometry configuration part R 1h-R 2-(3-R 3-4-R 4-5-R 5-6-R 6) C 5be dissolved in tetrahydrofuran (THF) at N – 78 DEG C ~ 0 DEG C, add normal hexane solution that concentration is the n-Butyl Lithium of 1.0 ~ 2.0mol/L successively, chemical formula is LnCl 3(thf) nthe rare earth trichloride of (n=2 ~ 3.5) and single anion ligand, described single anion ligand is CH 2siMe 3, CH (SiMe 3) 2, o-NMe 2-CH 2c 6h 4, 1,3-C 3h 5, 1,3-C 3h 4or 1,3-C (Me) 3h 3(SiMe 3) 2;
R 1for fluorenyl derivative C 13a 8, indenyl derivative C 9a 6or cyclopentadienyl derivative C 5a 4, A is selected from hydrogen;
R 2be selected from methylene radical, ethylidene or dimethyl silica-based;
R 3be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 4be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 5be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl;
R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl;
Ln is selected from Lu, Y or Sc;
4. preparation method according to claim 3, is characterized in that, the mol ratio of described constrained geometry configuration part, n-Butyl Lithium, rare earth trichloride and single anion ligand is 1:1:1:2.
5. a polymerization catalyst system, by the rare earth compounding described in claim 1 or 2, organic boron salt and alkylating reagent 1:(1 ~ 2 in molar ratio): (2 ~ 1000) form.
6. polymerization catalyst system according to claim 5, is characterized in that, described organic boron salt is [Ph 3c] [B (C 6f 5) 4], [PhNMe 2h] [BPh 4] or [PhNMe 2h] [B (C 6f 5) 4].
7. polymerization catalyst system according to claim 5, is characterized in that, described alkylating reagent is molecular formula is AlR 3aluminum alkyls, molecular formula be HAlR 2alkyl-al hydride, molecular formula be AlR 2the alkyl aluminum chloride of Cl or aikyiaiurnirsoxan beta.
8. polymerization catalyst system according to claim 7, it is characterized in that, described aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum;
Described alkyl-al hydride is dimethyl hydrogenated aluminium, ADEH, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dioctyl aluminum hydride;
Described alkyl aluminum chloride is dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-n-butyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dioctyl aluminum chloride;
Described aikyiaiurnirsoxan beta is methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta or normal-butyl aikyiaiurnirsoxan beta.
9. a polymerization catalyst system, by the rare earth compounding described in claim 1 or 2, organic boron salt, and triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium, diethylbenzyl aluminium, dicyclohexyl aluminum hydride, phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, ethyl p-methylphenyl aluminum hydride, dicyclohexyl aluminum chloride, phenylbenzene aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, any one 1:(1 ~ 2 in molar ratio in Ethylbenzyl chlorination aluminium and ethyl p-methylphenyl aluminum chloride): (2 ~ 1000) form.
10. be polymerized the preparation method with catalyst system, comprise the following steps:
By the rare earth compounding described in claim 1 or 2, organic boron salt and alkylating reagent 1:(1 ~ 2 in molar ratio): (2 ~ 1000) are at C 6~ C 7aromatic hydrocarbon solvent in mix, obtain polymerization catalyst system.
The preparation method of 11. 1 kinds of polystyrene, comprises the following steps:
Styrene monomer is added in the organic solution of the polymerization catalyst system described in claim 5 ~ 9 any one, the mol ratio of described styrene monomer and described rare earth compounding is (250 ~ 4000): polyreaction 1 ~ 30 minute at 1 – 20 ~ 80 DEG C, add ethanol solution hydrochloride and stop polyreaction, after sedimentation, drying, obtain polystyrene.
The preparation method of 12. 1 kinds of multipolymers, comprises the following steps:
Reaction monomers is added in the organic solution of the polymerization catalyst system described in claim 5 ~ 9 any one, described reaction monomers is the mix monomer of divinyl and cinnamic mix monomer or vinylbenzene and isoprene, the mol ratio of described reaction monomers and described rare earth compounding is (250 ~ 2000): polyreaction 5 ~ 60 minutes at 1 – 20 ~ 80 DEG C, add ethanol solution hydrochloride and stop polyreaction, after sedimentation, drying, obtain polymkeric substance.
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